Laboratory-polluted soils: a methodological approach to establish equilibrium conditions for different metal chemical forms in soils

An approach based on the number of extractions performed over time was applied to study the time necessary to attain equilibrium conditions between the different chemical forms present in two natural soils laboratory-loaded with heavy metals (Cu(II), Pb(II), Zn(II)). The influence of some soil parameters, such as pH value, cation exchange capacity and organic matter content, on the equilibrium time was evidenced both by the different nature of the soils and by the treatment of soils with paper mill sludge. Equilibrium conditions were determined by studying the metal partitioning in the soil on a case by case basis. The behaviour of the three metals was not the same, and the conditions of equilibrium among the different chemical forms were the result of the amount of heavy metals added as well as of the nature of the soil.     

Metal ion removal from water by sorption on paper mill sludge

Chromatographic columns packed with paper mill sludge are employed for metal ion recovery from water. The breakthrough curves show that cadmium, copper, lead and silver are removed from acid solutions (pH 2, 4); the affinity series is Pb(II)>Cu(II)>Ag(I)>Cd(II). Both the amount of metal retained and the metal-matrix interaction are pH dependent; the sorptive capacity increases with increasing pH. When the metals are present together at the same initial concentrations a competition among the different ions occurs although the affinity order remains unchanged. In metal recovery from the paper mill sludge column, the total amount of the cadmium and copper is displaced by HCl 1.0 M, 65% of the lead by HCl 0.1 M and 75% of the silver by HNO(3) 0.1 M. More than 95% of copper and lead and less than 20% of cadmium were recovered with HCl 0.1 M when the metals were present at the same time.     

Municipal landfill leachate-soil interactions: a kinetic approach

On investigating the effects of municipal landfill leachates on soils, it is found that the adsorption of landfill leachate constituents creates a "new" soil surface able to enhance heavy metal uptake. In particular, the treatment of soil with the total leachates led to an increase in its metal retention capability that was much higher than for each individual fraction. Results show that the leachate sorption on soil is regulated by the presence of leachate constituents with low molecular weight cut-off since these fractions are able to "accelerate" the sorption of higher molecular weight fractions. The rapidly sorbed lower molecular weight fractions create a different soil surface that is able to accommodate the high molecular weight constituents.     

Adsorption of phenols by papermill sludges

In this paper we studied the sorption capacity of paper mill sludges for phenols. Phenol, 2-chlorophenol (2-CP), 3-chlorophenol 3-CP). 4-chlorophenol (4-CP), 2-nitrophenol (2-NP), 4-nitrophenol (4-NP), 2.4-dichlorophenol (2,4-DCP), 3,4-dichlorophenol (3,4-DCP) 3,5-dichlorophenol (3,5-DCP) and 2,4,5-trichlorophenol (2,4,5-TCP) were chosen for the sorption tests. Kinetic experiments showed that substituted-phenol sorption on papermill sludge was rapid (equilibrium was reached after 3 h); conversely, the time taken by the phenol to reach equilibrium conditions was 260 h. Experimental data showed that particle diffusion was involved in the sorption process but was not the only rate-limiting mechanism; several other mechanisms were involved. The adsorption isotherms showed the following order of retention capacity of papermill sludge: 2-NP = 4-NP < < 2-CP < phenol < 4-CP < or = 3-CP < 2,4 DCP<3,4 DCP=2,4,5 TCP<3,5 DCP. In all cases the experimental data showed a good fit with the Hill equation. which is mathemratically equivalent to the Langmuir-Freundlich model obtained by assuming that the surface is homogeneous, and that the adsorption is a cooperative process influenced by adsorbate-adsorbate interactions.     

Metal speciation in sediments of polluted and non‐polluted lakes

A five‐step extraction procedure for metal speciation studies (copper, lead, nickel, manganese and zinc) was applied to the analysis of lake sediments characterised by different environmental features. A different partition of metals into the several metal forms was observed. Both the metal fraction sorbed or co‐precipitated on hydrous Mn‐oxides (especially lead and zinc) and that bound to organic matter (especially copper) are high in some samples. A prevalently anthropogenic origin of these metals may be hypothesised on the basis of existing knowledge of the equilibrium and change phenomena occurring among water, particulate and sediments. Conversely, the non‐solubilised forms of metals are abundant in the sediments of lakes that are certainly not polluted. The concentration of manganese is very high in the sediments of Antarctic lakes; sequential extractions show its lithogenic origin. In conclusion, a knowledge of the different types of metal associations in sediments and their percentage can facilitate understanding of both natural and anthropogenic metal enrichment of aquatic systems.     

Turbulent structures of buoyant jet in cross-flow studied through large-eddy simulation

Environmental Fluid Mechanics - In the present paper we study buoyant (plume) and non-buoyant (jet) fluid injection in a neutrally stratified uniform cross-flow. Both cases are of practical...     

Copper and other trace elements strongly bound to humic acids along sediment cores in the Ross Sea, Antarctica

Marine sediment cores sampled in three different areas, during the 1997/98 Italian Antarctic Expedition, were studied. The cores (40 cm) were immediately subdivided into 13 or 14 layers (2-4 cm) in order to obtain a high-depth resolution in the metal content and humic substance analyses. The results obtained for the amount of metals strongly bound to humic acids showed the following order: Cu > Zn > Co > As >or= Mn. The fraction of Cu, Zn and As bound to humic acid (microg g(-1) of HA) increases in the first 10-12 cm of cores, then a decrease is observed. This observation could be related both to the presence of a mobile fraction of metals in sediments successively bound to humic acids and to different structural features showed by humic acids along the cores, due to transformation processes. For the other metals a variable pattern along the cores was found.     

Transport and modification of humic substances present in Antarctic snow and ancient ice

We performed a study of fulvic acids extracted from fresh and aged snow, and from recent and ancient ice in Antarctica. The fresh snow samples were collected in coastal and inland sites to evaluate the influence of the distance from the sea on organic matter transport. Moreover, in a site (Melbourne Mountain) samples were collected at different heights to study the influence of altitude on transport. The obtained results showed that dissolved fulvic acid concentrations are influenced neither by distance nor by height while particulate fulvic acid concentrations are influenced by both parameters. Moreover, the results showed that fulvic acids transported for a long distance can undergo chemical modifications. Chemical modifications are better evidenced by the analysis of samples taken in trenches at different depth, which showed structural changes attributable to the loss of nitrogen-containing compounds and to an increase in aromatic character of the structures due to reduction and/or condensation processes. With ageing, the humification process proceeds with heavy carbon losses as demonstrated by results obtained from fulvic acids isolated from ice aged between twenty-five thousand and seventy thousand years.     

Evidence of earliest human occurrence in Europe: the site of Pirro Nord (Southern Italy)

Some flint lithic artifacts were discovered in the fissure fillings of the well-known Pirro Nord site (Apulia, Southern Italy). The lithic industry, composed by three cores and some flakes, has been found to be associated to an Early Pleistocene vertebrate fossil assemblage. The fossil association contains a wide range of micromammals, including Allophaiomys ruffoi and Episoriculus gibberodon and large mammals including Bison degiulii and Equus altidens together with African elements as the gelada baboon Theropithecus and the saber-toothed cat Megantereon whitei. It defines the latest Villafranchian chronological unit (Pirro Nord Faunal Unit) in the Western European mammal biochronology. The lithic industry of Pirro Nord represents the oldest occurrence of the genus Homo in Europe as it is attributable to a chronological interval between 1.3 and 1.7 Ma. This supports the hypothesis that the genus Homo, with Oldowaian technology, extended its range in Europe, probably from western Asia, during the first half of the Early Pleistocene. The new discovery from Pirro Nord changes the chronology of the first arrival of hominids in Europe and offers new perspectives in the debate about the human dispersal in the Early Pleistocene.     

Characteristics of different molecular weight fractions of organic matter in landfill leachate and their role in soil sorption of heavy metals.

We have characterised two kinds of municipal landfill leachates derived from 'old' and 'young' municipal waste landfills on the basis of the molecular weight distribution of the constituents, taking into account that the great variety of leachate constituents prevents any evaluation of the fate and of the role played by each component in the environmental impact. In the sample S1 (old leachate), the constituents were distributed over a wider range of molecular weights; high molecular weight fractions were present. In sample S2 (young leachate), the fractions are actually narrower at the lower molecular weights. The high molecular weight fractions of old leachates are found to be complex structures formed by condensed nuclei of carbons substituted by functional groups containing nitrogen, sulphur and oxygen atoms; the low molecular weight fractions of leachates are, instead, characterised by linear chains substituted by oxygenated functional groups such as carboxyl and/or alcoholic groups. After characterising each fraction we studied the role played by these fractions in the soil's capability for retaining heavy metals [copper (Cu) and cadmium(Cd)]. The Cd uptake increases only on the soil treated with sample S1 characterised by a higher pH value and by the presence of high molecular weight fractions. The Cu uptake also increases on the soil treated with sample S2, characterised by the sole presence of low molecular weight fractions. On the other hand, the metal adsorption tests performed on soil treated with the single fractions show that the amount of Cu and Cd retained by soil treated with the high molecular weight fractions of sample does not increase after 72 h of treatment and that the amount of Cu retained by the low molecular weight fractions of sample S1 and by the fractions of sample S2 increases, but does not justify the amount retained by soil treated with the total leachates.